Polyether series synthetic lubricating oil compositions

ABSTRACT

LUBRICANTING OIL COMPOSITION FOR AN ENGINE OIL IS OBTAINED BY ADDING A POLYOXYALKYLENE GLYCOL ETHER N-AMINE SUBSTITUTED SUCCINIMIDE TO A POLYOXYALKYLENE GLYCOL ETHER.

r: 3,746,645 Ice Patented July 17, 1973 3,746,645 pylene oxide orbutylene oxide alone and an aliphatic POLYETHER SE SYNTHETIC LUBRICATINGalcohol (ROH) or subjecting to a random or block-co- GIL QOMPOSITIPNSpolymerization two or more these oxides or ethylene oxide Masahim Sam),sagamlhara Yoshlhar Tamzakl Kama simultaneously and said alcohol and ifnecessary, the end kura, and Keiichi Furuta and Kenichiro Minagawa,Kawasaki, Japan, assignors to Nippon 011s and Fats 5 Company Limited,Tokyo, Japan OH group may be alkyl etherified.

Illustrative of the polyethers is butoxypolyoxypropylene No Drawing.Filed Nov. 26, 1971, Ser. No. 202,652 glycol having a mplecular i t of500 to 3,000 9 Claims priority, application Japan, D 4. 1970, tamed bythe addl'tlOl'l polymerization of propylene ox1de 45/107,264 and butanoland further alkoxypolyoxypropylene glycol Int. Cl. 010m 3/30 obtained byusing the aliphatic alcohols, such as meth- U.S. Cl. 252-515 A 4 Claimsanol, ethanol, propanol, 2-ethyl-hexanol, Ziegler alcohol and oxoalcohol known as derivatives of petroleum chem- ABSTRACT OF THEDISCLOSURE istry and the like, may be mentioned. In addition,alkoxypolyoxyethyleneoxypropylene glycol, alkoxypolyoxypro- 5pyleneoxybutylene glycol, alkoxypolyoxyethyleneoxypropyleneoxybutyleneglycol, butoxypolyoxypropylene glycol mono ether having the abovedescribed hydrocarbon groups may be cited. The present invention relatesto lubricating oil com- Polyether N-arnine substituted succinimides havethe positions obtained by compounding a polyether N-amine followingformula.

Lubricating oil composition for an engine oil is obtained by adding apolyoxyalkylene glycol ether N-amine substituted succinimide to apolyoxyalkylene glycol ether.

substituted succinimide to a polyether series synthetic In the aboveformula, R R R x, y, z and n have lubricating oil. the same meanings asin the above Formula 1, R' is Polyoxyalkylene glycol ethers (abridged aspolyether C H J (m is an integer of 1 to 18), R is C H (g hereinafter)have been broadly used as in petroleum series is 0 or an inte er of 1 to15) and R is hydrogen or a lubricating oil but have not been suitablefor engine oil hydrocarbon group of CgH2g+1 (f is 0 or an integer of 1of motorcars. This is because the additives compatible to 40 to 3) and pand s are an integer of 1 to 6. the polyethers have not been fullydeveloped as compared As the dispersant for petroleum series lubricatingoil, with the petroleum series lubricating oil. Accordingly, alkenylsuccini id h b k o b t th bwhen the polyethers containing no detergentor dispersant stances are not at all dissolved in the polyethers or evenare used for an engine Oil O mOtOrCaTS, hey are poor in if dissolved,these substances have no excellent cleaning the function for dispersingcompletely carbon, varnish and and dispersing ability. On the contrary,the compounds slag formed by the incomplete combustion of fuel into thehaving the above Formula 2 are different from the oil and suchsubstances deposit on piston ring groove or alkenylsuccinimides and havea compatibility with the clog the oil filter resulting into aninterference of the polyethers and a high cleaning and dispersingability. driving of engine. The amount of the compounds having the aboveFor- The inventors have found that when the polyether mula 2 added basedon the polyethers is CHI-10%. (by series lubricating oils are used as alubricating oil of weight), preferably (LS-5% by weight. In less than0.1% an internal combustion engine, for example, an engine the activityis low, while even if more than 10% is added, oil of motorcars, theexcellent lubricating activity can the property is not very improved. beattained by compounding the dispersant of the present The compoundshaving the above Formula 2 include invention which has a highcompatibility and does not alkoxypolyoxyalkylene glycol monoallyl etherN-amine form ashes, to the polyether and accomplished the presentsubstituted succinimide, alkoxypolyoxyalkylene glycol 8- invention.methallyl ether N-substituted succinimide and the like and Thepolyethers having a viscosity of a lubricating oil alkoxypolyoxyalkyleneglycols are the compounds cited have the following formula. in theComposition 1 of the polyethers of the base oil.

The polyether N-amine substituted succinimides R .fl H H OLZQH CH QLLCHQH O (PASI) having the above Formula 2 are produced in the L\ l )A I I ifollowing manner.

(1) Namely, olefin ether of alkoxypolyoxyalkylene glycol is reacted withmaleic anhydride and then with a poly- R and R are hydrogen orhydrocarbon groups of amine to f i i m 2m+1 0T k 2k1: a R3 and 4 re hyrogen or The above described olefin ethers are produced in the fvllkyl gp of J 2 +1, m 18 an integef 0f 1 t0 k following manner.Alkoxypolyoxyalkylene glycol is added 15 Integer 0f 3 t0 1' is allInteger 0f 1 and with metallic sodium or sodium methylate (CH ONa) x, y,z and n are 0 or an integer of 1 to 100. to convert the end OH groupinto ONa, to which a The polyethers having the above Formula 1 areobmonohaloolefin is reacted. The monohaloolefin has the tained bysubjecting to an addition polymerization profollowing formula.

X RCH: C=CHI action, the unreacted polyamine and the solvent are dis- Itilled off to obtain the product. The polvammes have the followingformula In the above formula, X is chlorine, bromine or iodine HQN CH-NH H and R and R have the same meanings as described L\ (8) above.Illustrative of the monohaloolefin is allyl chloride and includeethylenediamine, diethylenetriamine, triethyland B-methallyl chloride.enetetramine, tetraethylenepentamine, trimethylenedi- For example,butoxypolyoxypropylene glycol is reacted amine andtetramethylenediamine.

O (9) with allyl chloride. When PASI of the present invention is addedto the polyether, this dispersant shows an excellent lubricating crH OCH,CH-OH CHBONB property and cleaning and dispersing ability and doesnot 3 form ashes and is suitable for the use for an engine oil of aninternal combustion engine. C4H9O CHrCH-O-NB CH3OH The followingexamples are given for the purpose of H (4) illustration of thisinvention and are not intended as limitations thereof. C4H O(OH;CH-O -NaC1GH,OH=0H, In the examples, part and percent mean by weight.

EXAMPLE 1 7 Nae 100 parts of butoxypolyoxypropylene glycol allyl etherCH; (5) having a molecular weight of about 1,000 is added withAlternatively, an alcohol having the following Formula 6 105 Parts ofmaleic anhydride and Parts P y OH D (ditert.-butyl peroxide, made byNippon 0118 and Fats 40 Co., Ltd.) and the resulting mixture was reactedat 180- 1 190 C. for 5 hours to obtain butoxypolyoxypropylene ispolymerized with alkylene oxides and then the end OH glycol allyl ethersuccinic anhydride in a reaction ratio of group is reacted withalkylmonochloride (R' X) to .form more than 95%. an alkylethe 110 partsof said succinic anhydride is dissolved in 130 1 mole of the olefinether having the above Formula 5 parts of xylol and 10.5 parts oftetraethylenepentamine is is reacted with 1-7 moles, preferably l-3moles of maleic added dropwise thereto at 160 C. in 2 hours. Thereacanhydride at a temperature of ISO-230 C., preferably tion mixture iscured for 3 hours and then xylol and the 180-200 C. for 5-20 hours.unreacted polyamine are distilled olf to obtain 120 parts 0 ofbutoxypolyoxypropylene glycol allyl ether succinimide.

0.11,0(oH,oH-o- -orr2-0H=om era-cf EXAMPLE 2 5H: )n 0 100 parts oflauroxypolyoxyethyleneoxypropylene glycol methallyl ether (molar ratioof E0 to PO; 1:9) having a molecular weight of 1,200 is added with 12parts of 0 maleic anhydride and the mixture is reacted at 180-190 C. for20 hours. As the amine, 8.5 parts of methylene tetramine is used and thereaction is effected in the same CH: 11 manner as in Example 1 to obtain117 parts of lauroxypolyoxyethyleneoxypropylene glycol methallyl ethersuccinimide.

(7) EXAMPLE 3 Less than 2% by weight of organic peroxide may be Thereaction is effected in the same manner as described added as thereaction catalyst. In order to prevent the i Example 1 except thatmethoxypolyoxyethyleneoxythermal decomposition of the reaction product,the reacpropyleneoxybutylene glycol allyl ether (molar ratio of tion maybe effected in gaseous nitrogen by adding EOzPOzBO; 1:821) having amolecular weight of about xylol, toluene and the like as a dilutingsolvent. After the 1,000 is used and 5.0 parts of tetramethylenediamineis reaction, unreacted maleic anhydride and xylol are reused as thepolyamine, to obtain 114 parts of meth-oxymoved by a distillation undera reduced pressure. polyoxyethyleneoxypropyleneoxybutylene glycol allylThereafter, 1 mole of the compound having the above ether suceinimiddescribed Formula 7 is dissolved in xylol and then 1-7 I h example, E0is ethylene oxide, PO is propylene moles, preferably 1-3 moles of apolyamine is added id d B0 i b t l id thereto gradually and the reactionmixture is heated at 120-180 C. to effect dehydration while refluxingxylol, EXAMPLE 4 whereby imide is formed. The progress of the reactioncan The compositlon of samples of engine oil is shown in be observed bythe amount of water formed. After the rethe following Table l.

TABLE 1 Dispersant Polyether P-a-NA Sample Name Part Name (viscosity)Part (part) A Butgxypolyoxyprgpylene glycol allyl 2Butoxypolyoxypropylene glycol (SAE- iO). 96 2 e er succ e. BLauroxypolyoxyethyleneoxypropylene Lauroxypolyoxyethyleneoxypropylen 932 glycol methallyl ether succinimide. gsxoElggolar ratio of E0 to P0,1:9) 0 Methoxypolyoxyethyieneoxypro- 3 Methoxypolyoxyethyleneoxypro- 952 pyleneoxybutylene glycol allyl ether pyleneoxybutylene glycol (molarratio succinimide. EOzPOzBO, 1:8:1) (SAE-40). D N Butoxypolyoxypropyleneglye 98 2 P-a-NA is an antioxidant of phenyl-u-naphthyi amine.

Test manner The dispersant was added to an engine oil of motorcar andthe runnnig test was made. A common motorcar having a displacement of2,000 cc. was used and the running test was effected based on thefollowing standard of the exchange of the sample oil.

Sample oil A, B, C, D of the Table 1, fuel: L.P.G. Standard of exchange,30,000 kin/3 months.

Four new cars were charged with the sample oils separately and the carswere run under usual running condition and after about 240,000 km. wasrun for 2 years, each portion of the engine was checked based on C.R.C.estimation standard.

01 (molecular weight 1,200) (SAE-40).

having the following formula of 1-100, and n is an integer of l-100,(Ll-10% by weight of a polyoxyalkylene glycol ether N-amine substitutcdsuccinimide having the following formula R O CH CHO CH CHO CH CHO L i. Ml, M i, )1

Analysis of the sample oil cH=c-oH,-oH-o L After about 30,000 km. wasrun for 3 months, the 2 D J, total amount of oil was discharged andexchanged. The z analyzed value is shown in Table 2.

TABLE 2 Sample 011 A B C D Before After Before After Before After BeforeAfter Item use use use use use use Viscosity, 98.9 C. (0st.) 15. 6 15. 613. 6 Viscosity, 37.8 C. (cst.). 96. 5 99. 8 87. 1 Viscosity indexnumber-. 141. 0 139. 6 138. 8 PH (isopro water) 9. 1 4. 0 3. 4 Remainingcarbon, percent 1.3 1. 68 Heptane, insoluble percent portion- 2. 9 4. 5Carbon dispersibility Good Bad Oil element condition G d 1 1 Fairly bad.

NorE.Isopro water means a solution of 10 g. of sample dissolved in 60ml. of a mixture of isopropyl alcohol and water (mixture ratio ofisopropyl alcohol to water is 10:6 by volume).

The estimation of each portion of engine is shown in the following Table3.

TABLE 3 A B c D Running distance of sample Oil, km- 239, 372 236, 579230, 370 239, 671

Item:

Cleaning ability of piston:

Deposit of carbon on top ring groove Deposit on ring groo Deposit onring land.. Agglomeration on ring Deposit on piston crown Deposit onunder crown... Deposit on piston skirt.-.- Cleaning ability oflubricating oil tellillli No No No No wherein R R R x, y, z and n: havethe same meanings as described above, R' is C H i (m is an integer of1-18), R is C,;H;, (g is 0 or an integer of 1-15), R is hydrogen or ahydrocarbon group of C H (f is 0 or an integer of 1-3) and p and s arean integer of 1-6.

2. Polyether series synthetic lubricating oil composition as claimed inclaim 1, wherein the polyoxyalkylene glycol ether Nsubstitutedsuccinimide is butoxypolyoxypropylene glycol allyl ether succinimide.

3. Polyether series synthetic lubricating oil composition as claimed inclaim 1, wherein the polyoxyalkylene glycol ether N-substitutedsuccinimide is lauroxypolyoxyethyleneoxypropylene glycol methallyl ethersuccinimide.

4. Polyether series synthetic lubricating oil composition as claimed inclaim 1, wherein the polyoxyalkylene glycol ether N-substitutedsuccinimide is methoxypolyoxyethyleneoxypropyleneoxybutylene glycolallyl ether succinimide.

References Cited UNITED STATES PATENTS WERTEN F. W. BELLAMY, PrimaryExaminer Patent No. 3,7 6,6 5 Dated November 26, 1971 Inventor(s) IT ETAL It is eertified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 3, line 35 "NaC"" should be NaCl Column 3, line 56 "Cn"" shouldbe CH Column 6, Line nu "138.8"" should be 138.5 Column 6, line 5 "311'" should be 3.8

-'Column 6, line &6 "1.68"" should be' 1.6M Column 6, line- 47 1.5"should be u.8

- Signed and sealed this 29th day of October 1974.

(SEAL) Attest:

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner ofPatents

